2-methoxymethyl-2, 4-dimethyl-1, 5 pentanediol bis



United States Patent Office 2,853,498 Patented Sept. 23, 1958 2 METHOXYMETHYL 2,4 DIIMETHY L 1,5 PEN- TANEDIOL BIS-(3,4-EPOXYCYCLOHEXANE CAR- BOXYLATE) Benjamin Phillips and Paul S. Starcher, Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York 1 Claim. (Cl. 260-348) This invention relates to a new class of organic compounds which are useful in plastics and resins industry. More particularly, this invention relates to a new class of diepoxide compounds prepared from the cycloaliphatic esters of polyhydric compounds.

The compounds of this invention may be conveniently represented by the following general formula:

wherein R R R R R and R represent a hydrogen atom or an aliphatic hydrocarbon radical and R represents a divalent organic radical such as, for example, an aliphatic radical and an oxy-alkylene radical.

The compounds of this invention are useful as modifiers for commercially important synthetic condensation resins, and are particularly adapted for use as stabilizers and plasticizers for various synthetic organic resins, and in addition yield permanent, non-migrating compositions which are very valuable in certain commercial applications such as, for example, surface coatings, laminates and plastic molding compositions.

The compounds of this invention are produced by the epoxidation of the olefinic linkages contained in the starting material and may be prepared by either of two oxidation procedures, both of which are satisfactory and provide commercially acceptable yields.

The first oxidation method is called the acetaldehyde monoperacetate method and the reaction whereby the epoxides are formed may be illustrated by the following general equation:

acid method and the reaction whereby the epoxides are formed may be illustrated by the following general 7 equation:

PERACETIC ACID METHOD R: R2 R2 R2 R3 R1 R1 R3 C-OR-OC R0 R0 +CH COzOH 4 Ra R0 R4 R5 Ra Ra Rn (II) R2 R2 2 R2 R, R. 0 R. R!

-o R 0-o 0 R0 R0 0 CHQCOOH R R0 R0 R4 R5 R5 R5 R5 wherein R, R R R R R and R are as above defined.

The use of peracetic acid as the oxidation agent is particularly well suited for the epoxidation reaction since the cyclohexenyl ring is relatively easily converted to the corresponding epoxy form. This particular ability of the peracetic acid and other peracids, in general, to promote clean-cut reactions and provide acceptable yields is not unusual in the art of oxidizing organic compounds for it has long been recognized that the percarboxylic acids occupy somewhat of a unique position in the oxidizing reagent field since they are able to efiect several specific types of chemical transformations with acceptable efliciencies, while other powerful oxidizing reagents, such as potassium permanganate are not.

One such type of chemical transformation that the peracids are able to effect is that type of reaction which makes available the compounds of this invention, that is, the oxidation of unsaturated organic compounds to produce the corresponding epoxides.

The unsaturated cycloaliphatic carboxylic acids which are used in the preparation of the starting materials of this invention may be prepared by reacting butadiene or the homologues of butadiene with alpha, beta-unsaturated aliphatic aldehydes, such as, for example, acrolein, methacrolein, crotonaldehyde and the like to yield the corresponding unsaturated cycloaliphatic aldehyde which in turn may be subjected to known oxidation procedures to yield the corresponding unsaturated cycloaliphatic carboxylic acids. Typical unsaturated aldehydes suitable for use in preparing the cycloaliphatic acids are reported in the literature by Sobecki, Ben, 43, 1040 (1910); Diels and Alder, Ann, 460, 106, 121 (1928); Ann. 470, 62403 (1929) and in their U. S. Patent 1,944,731.

ACETALDEHYDE MONOPERACETATE METHOD R R1 R2 Ra Ra R1 Rl\ Ra OH 0 COR-0-O Ra R0 CH5C\ O-CH ---s 0-0 R4 Ra Ra R4 Rs Rs R9 R0 (I) R: I R2 R2 R: Hi I R1 Ra o-R-o-o l 0 Ra Rt 0 CHaCHO CHSCOOH R4 Ra 0 4 Ra Ra R: R5

wherein R R R R R and R represent a hydrogen These unsaturated cycloaliphatic carboxylic acids may atom or an aliphatic radical and R represents a divalent 7 be readily reacted with aliphatic dihydric compounds to organic radical.

The second oxidation method is called the peracetic yield the corresponding unsaturated cycloaliphatic diester of the aliphatic dihydric compound.

The following list sets forth series of dihydric alcohols which are suitable for use in preparing the compounds of this invention:

PARAFFIN GLYCOLS (A) 1,2-glycols:

Ethylene glycol Propane-1,2-diol (B) 1,3-glycols:

Propane-1,3-diol Pentane-2,4-diol 2,2-dimethyltrimethylene glycol 2-ethylhexanedio1-1,3

(C) 1,4-glycols:

Butane-1,4-diol 2-methylpentane-2,5-diol 3 -methylpentane-2,5-diol Hexane-l ,4-diol Hexane-2,5-diol 2,5 -dimethylhexane-2 ,5 -diol (D) 1,5-glycols:

Pentane-1,5-diol Hexane-1,5-diol 2-methoxymethyl-2,4-dimethyl pentane-l,5-diol 2-ethoxymethyl-2,4-dimethyl pentane-1,5-diol (E) Misc. glycols:

Octadecane-l, l2-diol UNSATURATED GLYCOLS Olefinic glycols: 1-butene-3 ,4-diol 2-butene-1,4-dio1 Diolefinic glycols: 1,5-hexadiene-3,4-dil 2,6-octadiene-4,5-diol Acetylenic glycols: Z-butyne-lA-diol 3 -hexyne-2,5-diol 2,5 -dimethyl-3 -hexyne-2,5-diol GLYCOL DERIVATIVES Polyethylene glycols: Diethylene glycol Triethylene glycol Dipropylene glycol Example 1.Preparari0n 0f diethylene glycol bis-(3,4- epoxycyclohexanecarboxylate) Two hundred and fifty grams of diethylene glycol bisl3-cyclohexenecarboxylate) were heated in a flask with agitation to 40 C. Then 833 grams of 21.3 percent solution of: pcracetic acid in acetone (177 grams, 2.33 mols of peracelic acid) were added dropwise over a period of two hours. The reaction solution was maintained at 40 C. by cooling with a cold water bath. After addition was complete, the reaction conditions were maintained for an additional four hours, whereupon an analysis indicated that all of the peracetic acid had been consumed.

After being stored at 11 C. for sixteen hours, the reaction solution was mixed with 2200 grams of ethylbenzene and the resulting solution distilled under reduced pressure at a maximum temperature of 50 C. After the low-boiling material had been stripped off, there were obtained 278 grams of residue product which analyzed 39.5 percent as diethylene glycol bis-(3,4-epoxycyclohexanecarboxylate) by determination for epoxide groups, 3.8 percent as unreacted diethylene glycol bis-(3-cyclohexenecarboxylate) by determination of double bonds, and 0.38 percent acidic impurities calculated as acetic acid. The yield of the diepoxide product was 89.5 percent of theory.

Example 2.Preparati0n of 2-ethyl-L3-hexanediol bis- (3,4-epoxycyclohexanecarboxylate) To one hundred and fifty-seven grams of 2-ethyl-1,3- hexanediol bis-(3-cyclohexenecarboxy1ate) (0.434 mol) there were added dropwise, over a period of one and onehalf hours, three hundred and thirty-eight grams of a 24.5 percent solution of peracetic acid in acetone (83 grams, 1.095 mols of peracetic acid). The reaction solution was stirred and kept at 22-25 C. by immersing the reaction flask in a cool water bath. After the addition was complete, the reaction conditions were maintained the same for four and one-half hours longer and then the solution was stored at l1 C. for sixteen hours. Analysis at the end of this time indicated 94 percent of the theoretical amount of peracetic acid had been consumed.

The reaction solution was then added dropwise to a still kettle containing 500 grams of ethylbenzene refluxing at 55 C. at 35 mm. of Hg pressure and during addition, acetic acid, peracetic acid, acetone, and ethylbenzene were distilled oil at the top of the kettle. After addition was complete, all low-boiling constituents were stripped 01f up to a temperature of C. at .3 mm. of Hg pressure. There was obtained, as residue product, 166 grams of a hazy viscous liquid which analyzed 86.8 percent as 2-ethyl-l,3-hexanediol bis-(3,4-epoxycycl0hexanecarboxylate) by analysis for epoxide groups and 10.2 percent as unreacted 2-ethyl-1,3-hexanediol bis-(3-cyclohexenecarboxylate) by analysis for double bonds. The yield of the diepoxide product was 84.3 percent of theory.

Example 3.-Preparati0n of diethylene glycol bis-(6- metlzyl-3,4-ep0xycyclohexanecarboxylate) Two hundred and ninety-seven grams of diethylene glycol bis-(6-methyl-3-cyclohexenecarboxylate) were added dropwise, over a two hour period, with stirring at a temperature of 25-30 C., to 670 grams of a 21.2 percent solution of peracetic acid in acetone (161 grams, 2.122 mols of peracetic acid). The reaction solution was maintained at the above-mentioned temperature by immersing the flask in a water bath and after addition was complete, the reaction conditions were maintained for an additional four hours whereupon the solution was stored for sixteen hours at 11 C.

The reaction solution was then fed dropwise into a still kettle containing 1000 grams of ethylbenzene refluxing at 45 C. at 35 mm. of Hg pressure and acetone, acetic acid, peracetic acid, and ethylbenzene were distilled oft. After addition was complete, the product was stripped of lowboiling constituents up to a kettle temperature of 90 C. at 2 mm. of Hg pressure. There was obtained as residue product, 330 grams of amber-colored viscous liquid which analyzed 86.4 percent purity as diethylene glycol bis-(6- methyl-3,4-epoxycyclohexanecarboxylate) by analysis for epoxide groups and 13.0 percent as unreacted diethylene glycol bis-(-rnethyl-3-cyclohexenecarhoxylate) by analysis for double bonds. The yield was 87.8 percent of theory.

Example 4.-Preparati0n 0f 3-methyl-1 ,S-pentanediol bis- (3 ,4-ep0xycycl0hexanecarb oxylate Six hundred sixty-three grams of a 24.0 percent solution of peracetic acid in acetone (159 grams, 2.097 mols,

of peracetic acid) were fed dropwise over a period of two hours ten minutes to 220 grams (0.839 mol) of B-methyl- 1,5-pentanediol bis-(3-cyclohexenecarboxylate) stirring at 20-50 C. After addition was complete, the solution was allowed to react under the same conditions for two and one-half hours longer, at which time analysis indicated that all of the peracetic acid had been consumed.

The reaction solution was stored at 11" C. for sixteen hours and then was fed dropwise into a still kettle containing 1000 grams of ethylbenzene refluxing at 45 C. at 35 mm. of Hg pressure. During the addition, acetone, acetic acid, peracetic acid, and ethylbenzene were distilled 01f at the top of the kettle. The product was stripped of lowboiling constituents to a kettle temperature of 90 C. at 2 mm. of Hg pressure and there were obtained 314 grams of light yellow viscous liquid residue product which analyzed 96.3 percent as pure 3-methyl-1,5-pentanediol bis- (3,4-epoxycyclohexanecarboxylate) by epoxide analysis, and 7.65 percent unreacted 3-methyl-1,5-pentanediol bis- (3-cyclohexenecarboxylate) by analysis for double bonds. The yield was 88.3 percent of theory.

Example 5. Preparation of 2 methoxymethyl 2,4- dimethyl-L5 pentanediol bis (3,4 epoxycyclohexanecarboxylate) Seven hundred forty-five grams of a 21.0 percent solution of peracetic acid in acetone (156 grams, 2.019 mols of peracetic acid) were fed dropwise over a period of three hours fifteen minutes to 264 grams (0.673 mol) of 2- methoxymethyl 2,4 dimethyl 1,5 pentanediol bis- (3-cyclohexenecarboxylate) stirring at 4050 C. After addition was complete, the reaction was allowed to proceed under the same conditions for three more hours and then stored for sixteen hours at 11 C.

The reaction solution was then fed dropwise into a still kettle containing 1800 grams of ethylbenzene refluxing at 45 C. at 35 mm. of Hg pressure. During the addition, acetone, acetic acid, peracetic acid and ethylbenzene were distilled off at the top of the kettle. The product was stripped of low-boiling constituents to a kettle temperature of 85 C. at 3 mm. of Hg pressure. There were obtained 274 grams of residue which was 72.5 percent 2- methoxymethyl 2,4 dimethyl 1,5 pentanediol bis- (3,4-epoxycyclohexanecarboxylate) by epoxide analysis and 6.0 percent unreacted 2-methoxy-2,4-dimethyl-1,5- pentanediol bis-(3-cyclohexenecarboxylate) by analysis for double bonds. The yield was 69.6 percent of theory.

Example 6.Preparali0n of triethylene glycol bis-(3,4- epoxycyclohexanecarboxylate) Nine hundred fifty-five grams of a 21.0 percent solution of peracetic acid in acetone (200 grams, 2.64 mols, of peracetic acid) were fed dropwise over a period of three hours fifteen minutes to 322 grams (0.88 mol) of triethylene glycol bis-(3-cyclohexenecarboxylate) with stirring. The reaction was very exothermic and the temperature of the reaction solution was maintained at 40-50 C. by immersing the flask in a cold water bath. After addition was complete, the reaction conditions were maintained for an additional two and one-half hours, at which time analysis indicated that all of the peracetic acid had been consumed.

The reaction solution was stored for sixteen hours at 11 C. and then added dropwise to a still kettle containing 2500 grams of ethylbenzene refluxing at 40 mm. of Hg pressure. Acetone, acetic acid, peracetic acid and ethylbenzene were distilled off at the top of the kettle during the addition and the kettle residue was finally stripped of low-boiling constituents up to 70 C. at 3 mm. of Hg pressure. There were obtained 355 grams of viscous liquid analyzing 79.6 percent as triethylene glycol bis(3,4- epoxycyclohexanecarboxylate) by epoxide group analysis and 8.1 percent unreacted triethylene glycol bis-(3-cyclohexenecarboxylate) by analysis for double bonds. The yield of diepoxide was 80.8 percent of theory.

Example 7.Prepamti0n of 1,5-pentanedial bis-(3,4- epoxycyclohexanecarboxylate) Nine hundred forty-five grams of a 21.0 percent solution of peracetic acid in acetone (198 grams, 2.61 mols, of peracetic acid) were fed dropwise over a period of two hours ten minutes to 278 grams (0.87 mol) of 1,5-pentanediol bis-(3-cyclohexenecarboxylate) with stirring at 40-50 C. The reaction conditions were maintained for an additional two hours and forty-five minutes after addition was complete and then the solution was stored for sixteen hours at l 1 C.

The reaction solution was added dropwise to a still kettle containing 2500 grams of ethylbenzene refluxing at 40 mm. of Hg pressure and acetone, acetic acid, peracetic acid, and ethylbenzene were distilled off at the top of the kettle. After addition was complete, all lowboiling constituents were stripped oil up to a kettle temperature of 70 C. at 3 mm. of Hg pressure. There were obtained 311 grams of residue product which analyzed 84.3 percent 1,5-pentanediol bis-(3,4-ep0xycyclohexanecarboxylate) by analysis for epoxide groups and 6.94 percent unreacted 1,5-pentanediol bis-(3-cyclohexenecarboxylate) by analysis for double bonds. The yield was 84.6 percent of theory.

Example 8.-Preparali0n of ethylene glycol bis-(3,4- epoxycyclohexnnecarboxylate) Sixteen hundred eighty grams of a 24.9 percent solution of peracetic acid in acetone (418 grams. 5.5 mols, of peracetic acid) were fed dropwise over a period of four hours to 613 grams (2.2 mols) of ethylene glycol bis-(3-cycl0hexenecarboxylate) with stirring at 35-40 C. On completion of the addition, the reaction was allowed to proceed under the same conditions for an additional four hours and then the reaction solution was stored for sixteen hours at l.l C. At this time, analysis showed that 98.8 percent of the peracetic acid had been consumed.

The reaction solution was dissolved in 1600 grams of ethylbenzene and then distilled to remove all low-boiling constituents up to a kettle temperature of 70 C. and 2 mm. of Hg pressure. There were obtained 614 grams of residue product which analyzed 83.8 percent as ethylene glycol bis-(3,l-epoxycyclohexanecarboxylate) by analysis for epoxide groups, 5.0 percent unreacted ethylene glycol bis-(3-cyclohexenecarboxylate) by analysis for double bonds, and 0.5 percent acidic impurities calculated as acetic acid. The yield was 75.4 percent of theory.

Example 9.Preparati0n of 1,6-hexunediol bis-(3.4- epoxyc'yclolzexanecarhoxy[are) Five hundred and eighty-four grams of 1,6-hexanediol bis-(3-cyclohexenecarboxylate) (1.75 mols) were placed in a flask and 1560 grams of a 25.5 percent solution of peracetic acid in acetone were added over a four hour period. The reaction was exothermic and the solution was maintained at 3540 C. by cooling with an ice water bath as required. After the addition was complete, the reaction conditions were maintained for an additional one hour.

The reaction solution was fed dropwise into a still kettle containing 1750 grams of ethylbenzene refluxing at 25 mm. of Hg pressure. Acetone, acetic acid, peracetic acid, and ethylbenzene were distilled elf at the head during the addition period. After all of the reaction solution had been added, the residue product was stripped of ethylbenzene and there were obtained 665 7 grams of product analyzing 88.6 percent as 1,6-hexane- Serial No. 385, d ber 8, 1953, now U. S. diol bis-(3,4-epoxycyc1ohexanecarboxylate) by analysis for epoxide groups and 3.5 percent as unreacted diene by What is Claimed iSI analysis for double bonds. The yield of diepoxide corre- 2'methoxymethYI'ZA'dImEthYI'Ls-pemanedlol sponded to 92 percent of theory 5 4-epoxycyclohexanecarboxylate).

This application is a division of copending application, No references cited. 

